Japan Priority Application 2001-273196, filed Sep. 10, 2001 including the specification, drawings, claims and abstract, is incorporated herein by reference in its entirety.
The present invention relates to an aromatic polyimide ester and a method for producing thereof.
In recent years, various engineering plastics are being developed, and especially; a thermotropic liquid crystalline polymer showing an optical anisotropy in molten state, and excellent mechanical property by having a mesogenic structure with highly oriented shows excellent moldability.
The liquid crystalline polymer is oriented by injection molding, and therefore, a coefficient of linear expansion in machine direction (MD) is very small, but a coefficient of linear expansion in a direction transverse to flow direction (TD) shows an approximately as large as coefficient of linear expansion of thermoplastic resins. Accordingly a dimensional stability in transverse direction was not necessarily satisfactory.
On the other hand, as resins having a small coefficient of linear expansion, polyimide resins were known, but it has a water absorbing property.
As such resins that have feature of both a liquid crystalline polymer and polyimide resin, polyimide ester resins having imide bond and ester bond in a polymer molecule are known (Japanese Patent Publication No. 8-16155 B, Japanese Patent Publication No. 8-19236 B, and Japanese Patent Publication No. 8-19237 B). Although polyimide ester resins have excellent property of having a small coefficient of linear expansion and small water absorbing property; they have poor heat resistance, and therefore they tend to decompose by heat when melting process was carried out.
An object of the present invention is to provide an aromatic polyimide ester having a small coefficient of linear expansion and small water absorbing property, and moreover excellent heat resistance.
The present inventors found that a polyimide ester in which a repeating unit of a formula (IV) is ester-bonded in addition to repeating units of following formulas (I), (II), and (III), has a small expansion coefficient and small water absorbing property; and moreover excellent heat resistance, and thus the present invention was completed.
Namely, the present invention provides an aromatic polyimide ester comprising:
a repeating unit represented by a following formula (I), 
a repeating unit represented by a following formula (II), 
(n represents 0 or 1)
a repeating unit represented by a following formula (III), 
and a repeating unit represented by a following formula (IV) 
(in the formulas, -A- represents xe2x80x94Oxe2x80x94 or COxe2x80x94, and is located in para-position or in meta position to an imide group, and X represents direct coupling, xe2x80x94Oxe2x80x94, or xe2x80x94SO2xe2x80x94.),
and all of the said repeating units mutually bonded with each other through ester-bonds.
Reference designator n in the formula (II) represents 0 or 1. A preferable repeating unit represented by the formula (II) is as follows; 
An aromatic polyimide ester of the present invention may include either of the units among them, and may include both of them by arbitrary ratios, and in view of a heat-resistance of resulted aromatic polymide, preferably may include only 
wherein n in the formula (II) is 1.
A prefereable repeating unit represented by the formula (III) is following unit; 
An aromatic polyimide ester of the present invention may include either units among them, and also may include both of them by arbitrary ratios.
Preferable repeating units represented by the formula (Iv) are the following repeating units wherein -A- is xe2x80x94COxe2x80x94; 
More repeating units represented by the formula IV) are the following units, wherein -A- is xe2x80x94O-preferable repeating units represented by the formula (IV) are the following repeating units, when -A- is xe2x80x94COxe2x80x94. 
In addition, an aromatic polyimide ester of the present invention may include one of any kind among them, and it may include two or more kinds of them by arbitrary ratios.
In view of heat resistance and availability, following units are preferable. 
A mole ratio of repeating units in an aromatic polyimide ester of the present invention is preferably (I)/((II)+(III)+(IV)) is 30/70 to 90/10, more preferably 40/60 to 80/20, and still more preferably 50/50  to 70/30. And it is preferable that (IV)/((I)+(II)+(III)) is 0.9/99.9 to 30/70, more preferably 0.5/99.5 to 20/80, and still more preferably 1/99  to 10/90.
When the mole ratio of the repeating unit is out of the above-mentioned range, heat resistance of aromatic polyimide may be deteriorated.
An aromatic polyimide ester of the present invention may be produced by the following methods. An aromatic polyimide ester of the present invention may be produced, for example, by reacting a compound represented by a following formula (Ixe2x80x2), 
(Y1 represents a hydrogen atom or R1 CO)xe2x80x94 (R1 represents a hydrocarbon group with carbon numbers of 1 to 4), Z1 represents a hydrogen atom or a hydrocarbon group with carbon numbers of 1 to 4)
a compound represented by a following formula (IIxe2x80x2), 
(n represents 0 or 1, Y2 represents a hydrogen atom or R2CO(where R2 represents a hydrocarbon group with a carbon number of 1 to 4), Y3 represents a hydrogen atom or R3COxe2x80x94 (where R3 represents a hydrocarbon group with carbon numbers of 1 to 4))
a compound represented by a following formula (IIIxe2x80x2), 
(Z2 and Z3 represent independently a hydrogen atom or a hydrocarbon group with carbon numbers of 1 to 4 respectively, and Z3-Oxe2x80x94 CO-group is located in para-position or in meta position to Z2xe2x80x94Oxe2x80x94CO-group) and a compound represented by a following formula (IVxe2x80x2-1, (IVxe2x80x2-2), or 
(Y4 represents a hydrogen atom or R4COxe2x80x94 (where R4 represents a hydrocarbon group with carbon numbers of 1 to 4), Y5 represents a hydrogen atom or R5COxe2x80x94 (where R5 represents a hydrocarbon group with carbon numbers of 1 to 4), and Y4-A-group is located in para-position or in meta position to Y5-A-group.)
In a mole ratio of each compounds, (Ixe2x80x2)/[(IIxe2x80x2)+(IIIxe2x80x2)+{one of (IVxe2x80x2-1), (IVxe2x80x2-2) or (IVxe2x80x2-3)}] is preferably 30/70  to 90/10, more preferably 40/60 to 80/20, and still more preferably 50/50 to 70/30. And it is referable that {one of (IVxe2x80x2-1), (IVxe2x80x2-2) or (IVxe2x80x23)}/((Ixe2x80x2)+((IIxe2x80x2)+(IIIxe2x80x2) is preferably 0.1/99.9 to 30/70, more preferably 0.5/99.5 to 20/80, and still more preferably 1/99 to 10/90.
In the above-mentioned formulas (Ixe2x80x2), (IIxe2x80x2), (IIIxe2x80x2), (IVxe2x80x2-1), (IVxe2x80x2-2), and (IVxe2x80x2-3), Y1 represents a hydrogen atom or R1COxe2x80x94, Y2 a hydrogen atom or R2COxe2x80x94, Y4 a hydrogen atom or R3COxe2x80x94, Y4 a hydrogen atom or R3COxe2x80x94, and Y5 a hydrogen atom or R4COxe2x80x94, respectively.
Here, R1, R2, R3, R4, and R5 represent a hydrocarbon group with carbon numbers of 1 to 4, respectively. These hydrocarbon groups involve methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl, tert-butyl, etc. for example, and methyl group is preferable.
In addition, all of R1, R2, R3, R4, and R5 may be the same, some of them may be the same and others may be different, or all of them may be mutually different from others.
Z1, Z2, Z3, Z4, and Z5 represent a hydrogen atom or a hydrocarbon group with carbon numbers of 1 to 4, respectively. As the hydrocarbon group, the same as the above-mentioned groups may be mentioned. As Z1, Z2, Z3, Z4, and Z5, a hydrogen atom is preferable. In addition, all of Z1, Z2, Z3, Z4, and Z5 may be the same, some of them may be the same and others may be different, or all of them may be mutually different from others.
As compound represented by the formula (Ixe2x80x2), 4-acyloxy benzoic acid obtained by acylating 4-hydroxy benzoic acid using R1COOH(R1 represents the same group as the above-mentioned groups) or derivative thereof, 4-hydroxy benzoate ester or 4-acyloxy benzoate ester obtained by esterification of 4-hydroxy benzoic acid or 4-acyloxy benzoic acid with Z1O H (Z1 represents the same group as the above-mentioned groups) may be mentioned.
As examples of a compound represented by the formula (Ixe2x80x2), for example, 4-hydroxy benzoic acid, 4-hydroxy methyl benzoate, 4-hydroxy ethyl benzoate, 4-hydroxy butyl benzoate, etc. may be mentioned, and 4 hydroxy benzoic acid and 4-acetoxy benzoic acid are preferable.
These compounds may be used independently, or in combination of two or more kinds of them.
As examples of a compound represented by the formula (IIxe2x80x2), for example, 4-acyloxy phenols, such as hydroquinone, 4-acetoxy phenol, and 4-propionyl oxy phenol; 1,4-diacyloxy benzenes, such as 1,4diacetoxy benzene; 4xe2x80x2-acyloxy-4-hydroxy biphenyls, such as 4,4xe2x80x2-dihydroxy biphenyl, and 4xe2x80x2-acetoxy-4-hydroxy biphenyl; 4,4xe2x80x2-diacyloxy biphenyl, such as 4,4xe2x80x2-diacetoxy biphenyl may be mentioned. Among them, 4,4xe2x80x2-dihydroxy biphenyl and 4,4xe2x80x2diacetoxy biphenyl are preferable.
These compounds may be used independently, or in combination of two or more kinds of them.
As compounds represented by the formula (IIIxe2x80x2), for example, compounds obtained by esterifying terephthalic acid and isophthalic acid, or each of them using Z2OH, or Z3OH (Z2 and Z5 represent the same group as the above-mentioned groups) may be mentioned.
As examples of a compound represented by the formula (IIIxe2x80x2), for example, terephthalic acid monoesters, such as terephthalic acid, isophthalic acid, monomethyl terephthalate, monoethyl terephthalate, monopropyl terephthalate, and monobutyl terephthalate; terephthalic acid diesters, such as a dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, and dibutyl terephthalate; isophthalic acid monoesters, such as monomethyl isophthalate, monoethyl isophthalate, monopropyl isophthalate, and monobutyl isophthalate; isophthalic acid diesters, such as dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, and dibutyl isophthalate, etc. may be mentioned. Among them, terephthalic add and an isophthalic acid are preferable.
These compounds may be used independently, or in combination of two or more kinds of them.
As examples of a compound represented by the formula (IVxe2x80x2-1), for example, following compounds may be mentioned; N-(4-hydroxy phenyl or 4-acyloxy phenyl)-Nxe2x80x2-(4-hydroxy phenyl or 4-acyloxy phenyl) -biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimides, such as, N,Nxe2x80x2-bis(4-hydroxy phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2bis(4-acetoxy phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(4-propionyl oxy phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-hydroxy phenyl)-Nxe2x80x2-(4-acetoxy phenyl)-biphenyl-3,4,3xe2x80x2, 4xe2x80x2- tetra carboxylic acid diimide; N-(3-hydroxy phenyl or 3-acyloxy phenyl)-Nxe2x80x2(3-hydroxy phenyl or 3- acyloxy phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N,Nxe2x80x2-bis(3-hydroxy phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(3-acetoxy phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(3-propionyl oxy phenyl)-biphenyl3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(3-hydroxy phenyl)-Nxe2x80x2-(3-acetoxy phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide; N-(4-hydroxy phenyl or 4-acyloxy phenyl)-Nxe2x80x2-(3-hydroxy phenyl or 3-acyloxy phenyl)biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N-(4-hydroxy phenyl)-Nxe2x80x2-(3-acetoxy phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-acetoxy phenyl)-Nxe2x80x2-(3-acetoxy phenyl)-biphenyl-3,4,3xe2x80x2, 4xe2x80x2-tetra carboxylic acid diimide, N-(4-hydroxy phenyl)-Nxe2x80x2-(3-acetoxy phenyl)15 biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide; N-(4-hydroxy phenyl or 4-acyloxy phenyl)-Nxe2x80x2-(4-hydroxy phenyl or 4-acyloxy phenyl)-phenyl ether -3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N,Nxe2x80x2-bis(4-hydroxy phenyl)-phenyl ether-3,4,3,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(4-acetoxy phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(4-propionyl oxy phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-hydroxy phenyl)-Nxe2x80x2-(4-acetoxy phenyl)-phenyl ether -3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide; N-(3-hydroxy phenyl or 3-acyloxy phenyl)-Nxe2x80x2-(3-hydroxy phenyl or 3-acyloxy phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N,Nxe2x80x2-bis(3-hydroxy phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(3-acetoxy phenyl)phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(3-propionyl oxy phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(3-hydroxy phenyl)-Nxe2x80x2-(3-acetoxy phenyl)-phenyl ether-3,4,3xe2x80x2, 4xe2x80x2-tetra carboxylic acid diimide; N-(4-hydroxy phenyl or 4-acyloxy phenyl)-Nxe2x80x2-(3-hydroxy phenyl or 3-acyloxy phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N-(4-hydroxy phenyl)-Nxe2x80x2-(3-acetoxy phenyl)-phenyl ether 3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-acetoxy phenyl)-Nxe2x80x2-(3-acetoxy phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-hydroxy phenyl)-Nxe2x80x2-(3-acetoxy phenyl)-phenyl ether -3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide; N-(4-hydroxy phenyl or 4-acyloxy phenyl)-Nxe2x80x2-(4-hydroxy phenyl or 4-acyloxy phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N,Nxe2x80x2-bis(4-hydroxy phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(4-acetoxy phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(4-propionyl oxy phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-hydroxy phenyl)-Nxe2x80x2-(4-acetoxy phenyl)-phenyl sulfide -3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide; N-(3-hydroxy phenyl or 3-acyloxy phenyl)-Nxe2x80x2-(3-hydroxy phenyl or 3-acyloxy phenyl)-phenyl sulfide -3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N,Nxe2x80x2-bis(3-hydroxy phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(3-acetoxy phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(3-propionyl oxy phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(3-hydroxy phenyl)-Nxe2x80x2-(3-acetoxy phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide; N-(4-hydroxy phenyl or 4-acyloxy phenyl)-Nxe2x80x2-(3-hydroxy phenyl or 3-acyloxy phenyl)-phenyl sulfide -3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N-(4-hydroxy phenyl)-Nxe2x80x2(3-acetoxy phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-acetoxy phenyl)-Nxe2x80x2-(3-acetoxy phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-hydroxy phenyl)-Nxe2x80x2-(3-acetoxy phenyl)phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide; N,Nxe2x80x2-bis(4-hydroxy phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(4-acetoxy phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(4-propionyl oxy phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-hydroxy phenyl)-Nxe2x80x2-(4-acetoxy phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide; N-(3-hydroxy phenyl or 3-acyloxy phenyl)-Nxe2x80x2-(3-hydroxy phenyl or 3-acyloxy phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N,Nxe2x80x2-bis(3-hydroxy phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(3-acetoxy phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(3-propionyl oxy phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(3-hydroxy phenyl)-Nxe2x80x2-(3-acetoxy phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide; N-(4-hydroxy phenyl or 4-acyloxy phenyl)-Nxe2x80x2-(3-hydroxy phenyl or 3-acyloxy phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N-(4-hydroxy phenyl)-Nxe2x80x2(3-acetoxy phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-acetoxy phenyl)-Nxe2x80x2-(3-acetoxy phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-hydroxy phenyl)-Nxe2x80x2-(3-acetoxy phenyl)phenyl sulfone-3,4,3xe2x80x2, 4xe2x80x2-tetra carboxylic acid diimide; N-(4-carboxy phenyl or 4-alkoxy phenyl)-Nxe2x80x2-(4-carboxy phenyl or 4-alkoxy phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N,Nxe2x80x2-bis(4-carboxy phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(4-methoxy carbonyl phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(4-ethoxy carbonyl phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-carboxy phenyl)-Nxe2x80x2-(4-methoxy carbonyl phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide N-(3-carboxy phenyl or 3-alkoxy phenyl)-Nxe2x80x2-(3-carboxy phenyl or 3-alkoxy phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N,Nxe2x80x2-bis(3-carboxy phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(3-methoxy carbonyl phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(3-ethoxy carbonyl phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(3-carboxy phenyl)-Nxe2x80x2-(3-methoxy carbonyl phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide; N-(4-carboxy phenyl or 4-alkoxy phenyl)-Nxe2x80x2-(3-carboxy phenyl or 3-alkoxy phenyl)biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as N-(4-carboxy phenyl)-Nxe2x80x2-(3-carboxy phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-methoxy carbonyl phenyl)-Nxe2x80x2-(3-methoxycarbonyl phenyl)biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-carboxy phenyl)-Nxe2x80x2(3-methoxycarbonyl phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide; N-(4-carboxy phenyl or 4-alkoxy phenyl)-Nxe2x80x2-(4-carboxy phenyl or 4-alkoxy phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N,Nxe2x80x2-bis(4-carboxy phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(4-methoxycarbonyl phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(4-ethoxy carbonyl phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-carboxy phenyl)-Nxe2x80x2-(4-methoxy carbonyl phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide N-(3-carboxy phenyl or 3-alkoxy phenyl)-Nxe2x80x2-(3-carboxy phenyl or 3-alkoxy phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N,Nxe2x80x2-bis(3-carboxy phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(3-methoxy carbonyl phenyl)-phenyl ether 3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(3-ethoxy carbonyl phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(3-carboxy phenyl)-Nxe2x80x2-(3-methoxy carbonyl phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide; N-(4-carboxy phenyl or 4-alkoxy phenyl)-Nxe2x80x2-(3-carboxy phenyl or 3-alkoxy phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N-(4-carboxy phenyl)-Nxe2x80x2-(3-carboxy phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-methoxycarbonyl phenyl)-Nxe2x80x2-(3-methoxycarbonyl phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-carboxy phenyl-Nxe2x80x2-(3-methoxy carbonyl phenyl)-phenyl ether-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide N-(4-carboxy phenyl or 4-alkoxy phenyl)-Nxe2x80x2-(4-carboxy phenyl or 4-alkoxy phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N,Nxe2x80x2-bis(4-carboxy phenyl)-phenyl sulfide-3,4,8xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(4methoxycarbonyl phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(4-ethoxy carbonyl phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-carboxy phenyl)-Nxe2x80x2-(4-methoxy carbonyl phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide; N-(3-carboxy phenyl or 3-alkoxy phenyl)-Nxe2x80x2(3-carboxy phenyl or 3-alkoxy phenyl)phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N,Nxe2x80x2-bis(3-carboxy phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(3-methoxycarbonyl phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(3-ethoxy carbonyl phenyl)-phenyl sulfide-3,4,3xe2x80x2, 4xe2x80x2-tetra carboxylic acid diimide, N-(3-carboxy phenyl)-Nxe2x80x2-(3 methoxy carbonyl phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide; N-(4-carboxy phenyl or 4-alkoxy phenyl)-Nxe2x80x2-(3-carboxy phenyl or 3-alkoxy phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N-(4-carboxy phenyl)-Nxe2x80x2-(3-carboxy phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-methoxy carbonyl phenyl)-Nxe2x80x2(3-methoxy carbonyl phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-carboxy phenyl)-Nxe2x80x2-(3-methoxy carbonyl phenyl)-phenyl sulfide-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide; N-(4-carboxy phenyl or 4-alkoxy phenyl)-Nxe2x80x2-(4-carboxy phenyl or 4-alkoxy phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N,Nxe2x80x2-bis(4-carboxy phenyl)phenyl sulfone 3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(4-methoxy carbonyl phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(4-ethoxy carbonyl phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-carboxy phenyl)-Nxe2x80x2-(4-methoxy carbonyl phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide N-(3-carboxy phenyl or 3-alkoxy phenyl)-Nxe2x80x2-(3-carboxy phenyl or 3-alkoxy phenyl)phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N,Nxe2x80x2-bis(3-carboxy phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(3-methoxycarbonyl phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(3-ethoxy carbonyl phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(3-carboxy phenyl)-Nxe2x80x2-(3-methoxy carbonyl phenyl)-phenyl sulfone 3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide; N-(4-carboxy phenyl or 4-alkoxy phenyl)-Nxe2x80x2-(3-carboxy phenyl or 3-alkoxy phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, such as, N-(4-carboxy phenyl)-Nxe2x80x2-(3-carboxy phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-methoxy carbonyl phenyl)-Nxe2x80x2(3-methoxy carbonyl phenyl) phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N-(4-carboxy phenyl)-Nxe2x80x2-(3-methoxy carbonyl phenyl)-phenyl sulfone-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide.
Among these, in view of reactivity and heat-resistance, N,Nxe2x80x2-bis(4-hydroxy phenyl) biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(4-acetoxy phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide, N,Nxe2x80x2-bis(4-propionyl oxy phenyl)-biphenyl-3,4,3xe2x80x2,4xe2x80x2-tetra carboxylic acid diimide are preferable.
As examples of compound (IVxe2x80x2-2) or (IVxe2x80x2-3), following compounds may be mentioned, for example, 4,4xe2x80x2-bis(4-hydroxy phenyl amino carbonyl)-biphenyl-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(3-hydroxy phenyl amino carbonyl)-biphenyl-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(4-acetoxy phenyl amino carbonyl)-biphenyl 3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(3-acetoxy phenyl amino carbonyl)-biphenyl-3,3xe2x80x2-dicarboxylic acid, 4-(4-hydroxy phenyl amino carbonyl)-4xe2x80x2-(3-hydroxy phenyl amino carbonyl)-biphenyl-3,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(4-hydroxy phenyl amino carbonyl)-biphenyl-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(3-hydroxy phenyl amino carbonyl)biphenyl-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(4-acetoxy phenyl amino carbonyl)-biphenyl-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(3-acetoxy phenyl amino carbonyl)-biphenyl-4,3xe2x80x2-dicarboxylic acid, 3xe2x80x2-(4-hydroxy phenyl amino carbonyl)-4xe2x80x2-(3-hydroxy phenyl amino carbonyl)-biphenyl-3,4xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(4-hydroxy phenyl amino carbonyl)-phenyl ether-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(3-hydroxy phenyl amino carbonyl)-phenyl ether-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(4-acetoxy phenyl amino carbonyl)-phenyl ether-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(3-acetoxy phenyl amino carbonyl)phenyl ether-3,3xe2x80x2-dicarboxylic acid, 4-(4-hydroxy phenyl amino carbonyl)4xe2x80x2-(3-hydroxy phenyl amino carbonyl)-phenyl ether-3,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(4-hydroxy phenyl amino carbonyl)-phenyl ether-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(3-hydroxy phenyl amino carbonyl)-phenyl ether-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(4-acetoxy phenyl amino carbonyl)-phenyl ether-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(3-acetoxy phenyl amino carbonyl)-phenyl ether-4,3xe2x80x2-dicarboxylic acid, 3xe2x80x2-(4-hydroxy phenyl amino carbonyl)-4xe2x80x2-(3-hydroxy phenyl amino carbonyl)-phenyl ether-3,4xe2x80x2-dicarboxylic acid, 4,4xe2x80x2bis(4-hydroxy phenyl amino carbonyl)-phenyl sulfide-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(3-hydroxy phenyl amino carbonyl)-phenyl sulfide-3,3-dicarboxylic acid, 4,4xe2x80x2-bis(4-acetoxy phenyl amino carbonyl)-phenyl sulfide-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(3-acetoxy phenyl amino carbonyl)phenyl sulfide-3,3xe2x80x2-dicarboxylic acid, 4-(4-hydroxy phenyl amino carbonyl)-4xe2x80x2-(3-hydroxy phenyl amino carbonyl)-phenyl sulfide-3,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(4-hydroxy phenyl amino carbonyl)-phenyl sulfide-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(3-hydroxy phenyl amino carbonyl)phenyl sulfide-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(4-acetoxy phenyl amino carbonyl)-phenyl sulfide-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(3-acetoxy phenyl amino carbonyl)-phenyl sulfide-4,3xe2x80x2-dicarboxylic acid, 3xe2x80x2-(4-hydroxy phenyl amino carbonyl)-4xe2x80x2-(3-hydroxy phenyl amino carbonyl)-phenyl sulfide-3,4xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(4-hydroxy phenyl amino carbonyl)phenyl sulfone-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(3-hydroxy phenyl amino carbonyl)-phenyl sulfone-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(4-acetoxy phenyl amino carbonyl)-phenyl sulfone-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(3-acetoxy phenyl amino carbonyl)-phenyl sulfone-3,3xe2x80x2-dicarboxylic acid, 4-(4-hydroxy phenyl amino carbonyl)-4xe2x80x2-(3-hydroxy phenyl amino carbonyl)phenyl sulfone-3,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(4-hydroxy phenyl amino carbonyl)-phenyl sulfone-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(3-hydroxy phenyl amino carbonyl)-phenyl sulfone-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(4-acetoxy phenyl amino carbonyl)-phenyl sulfone-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(3-acetoxy phenyl amino carbonyl)-phenyl sulfone-4,3xe2x80x2-dicarboxylic acid, 3xe2x80x2(4-hydroxy phenyl amino carbonyl)-4xe2x80x2-(3-hydroxy phenyl amino carbonyl)phenyl sulfone-3,4xe2x80x2-dicarboxylic acid.
4,4xe2x80x2-bis(4-carboxy phenyl amino carbonyl)-biphenyl-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(3-carboxy phenyl amino carbonyl)-biphenyl-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(4-methoxycarbonyl phenyl amino carbonyl)-biphenyl-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(3-methoxycarbonyl phenyl amino carbonyl)-biphenyl-3,3xe2x80x2-dicarboxylic acid, 4-(4-carboxy phenyl amino carbonyl)-4xe2x80x2-(3-carboxy phenyl amino carbonyl)-biphenyl -3,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(4-carboxy phenyl amino carbonyl)biphenyl-4,3xe2x80x2-dicarboxylic acid, 3,4-bis(3-carboxy phenyl amino carbonyl)biphenyl-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(4-methoxycarbonyl phenyl amino carbonyl)-biphenyl-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(3-methoxycarbonyl phenyl amino carbonyl)-biphenyl-4,3xe2x80x2-dicarboxylic acid, 3xe2x80x2-(4-carboxy phenyl amino carbonyl)-4xe2x80x2-(3-carboxy phenyl amino carbonyl)-biphenyl -3,4xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(4-carboxy phenyl amino carbonyl)-phenyl ether-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(3-carboxy phenyl amino carbonyl)phenyl ether-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(4-methoxycarbonyl phenyl amino carbonyl)-phenyl ether-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(3-methoxycarbonyl phenyl amino carbonyl)-phenyl ether-3,3xe2x80x2-dicarboxylic acid, 4-(4-carboxy phenyl amino carbonyl)-4xe2x80x2-(3-carboxy phenyl amino carbonyl)-phenyl ether-3,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(4-carboxy phenyl amino carbonyl)-phenyl ether-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(3-carboxy phenyl amino carbonyl)-phenyl ether-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(4-methoxy carbonyl phenyl amino carbonyl)-phenyl ether-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(3-methoxycarbonyl phenyl amino carbonyl) phenyl ether-4,3xe2x80x2-dicarboxylic acid, 3xe2x80x2-(4-carboxy phenyl amino carbonyl)-4xe2x80x2-(3-carboxy phenyl amino carbonyl)-phenyl ether 3,4xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(4-carboxy phenyl amino carbonyl)-phenyl sulfide-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(3-carboxy phenyl amino carbonyl)-phenyl sulfide-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(4-methoxycarbonyl phenyl amino carbonyl)-phenyl sulfide-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(3-methoxycarbonyl phenyl amino carbonyl)-phenyl sulfide-3,3xe2x80x2-dicarboxylic acid, 4-(4-carboxy phenyl amino carbonyl)-4xe2x80x2-(3-carboxy phenyl amino carbonyl)-phenyl sulfide-3,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(4-carboxy phenyl amino carbonyl)-phenyl sulfides 4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(3-carboxy phenyl amino carbonyl)phenyl sulfides-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(4-methoxycarbonyl phenyl amino carbonyl)-phenyl sulfides-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(3-methoxycarbonyl phenyl amino carbonyl)-phenyl sulfide-4,3xe2x80x2-dicarboxylic acid, 3xe2x80x2-(4-carboxy phenyl amino carbonyl)-4xe2x80x2-(3-carboxy phenyl amino carbonyl)-phenyl sulfide-3,4xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(4-carboxy phenyl amino carbonyl)-phenyl sulfone-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(3-carboxy phenyl amino carbonyl)-phenyl sulfone-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(4-methoxycarbonyl phenyl amino carbonyl)-phenyl sulfone-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(3-methoxycarbonyl phenyl amino carbonyl)-phenyl sulfone -3,3xe2x80x2-dicarboxylic acid, 4xe2x80x2(4-carboxy phenyl amino carbonyl)-4xe2x80x2-(3-carboxy phenyl amino carbonyl)-phenyl sulfone-3,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(4-carboxy phenyl amino carbonyl)-phenyl sulfone-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(3-carboxy phenyl amino carbonyl)-phenyl sulfone-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(4-methoxy carbonyl phenyl amino carbonyl)phenyl sulfone-4,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(3-methoxy carbonyl phenyl amino carbonyl)-phenyl sulfone-4,3xe2x80x2-dicarboxylic acid, 3xe2x80x2-(4-carboxy phenyl amino carbonyl)-4xe2x80x2-(3-carboxy phenyl amino carbonyl)-phenyl sulfone-3,4xe2x80x2-dicarboxylic acid, etc. may be mentioned.
These compounds may be used independently, or in combination of two or more kinds of them.
Among them, in view of reactivity, availability, and heat resistance, 4,4xe2x80x2-bis(4-hydroxy phenyl amino carbonyl)-biphenyl-3,3xe2x80x2-dicarboxylic acid, 4,4xe2x80x2-bis(4-acetoxy phenyl amino carbonyl) biphenyl-3,3xe2x80x2-dicarboxylic acid, 3,4xe2x80x2-bis(4-hydroxy phenyl amino carbonyl)biphenyl-4,3xe2x80x2-dicarboxylic acid, and 3,4xe2x80x2-bis(4-acetoxy phenyl amino carbonyl)-biphenyl-4,3xe2x80x2-dicarboxylic acid are preferable.
The above-mentioned compound (IVxe2x80x2-2) or (IVxe2x80x2-3) is obtained by reacting a compound represented by a formula (A) 
(X represents direct bond, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, and SO2xe2x80x94), with a compound represented by a general formula (B). 
(in the formula, m represents 0 or 1, Z represents the same group as the above-mentioned Z4 or Z5, and, amino group is located in para-position or 
meta position to above group (Bxe2x80x2).).
As a compound (B), for example, p- or m-aminophenol, p- or m-acyloxy aniline, p- or m-aminobenzoic acid or an ester thereof, etc. may be mentioned.
A compound (IVxe2x80x2-l) may be obtained by dehydrating and cyclizing (imide cyclization) a compound (IVxe2x80x2-2) or (IVxe2x80x2-3) produced by the above-mentioned method. In addition, a compound (IVxe2x80x2-2) or (IVxe2x80x2-3) may be obtained by hydrolyzing a compound (IVxe2x80x2-1).
A reaction of the above-mentioned compound (A) and (B) easily proceed by mixing both components preferably in a state of solution to form a compound (IVxe2x80x2-2) or (IVxe2x80x2-3). A reaction temperature of the reaction is usually xe2x88x9250 to 200xc2x0 C., and is preferably 50 to 150xc2x0 C.
Various methods may be used in dehydration and cyclization of the compound (IVxe2x80x2-2) or (IVxe2x80x2-3). For example, following methods may be mentioned:
(1) a method in which cyclodehydration is performed under coexistence of carboxylic acid anhydride;
(2) a method in which cyclodehydration is performed by inorganic acid or condensate thereof having dehydrating ability;
(3) a method in which in the presence of acid catalyst cyclodehydration is performed in azeotropic state;
(4) a method in which cyclization is performed using special dehydrating agent;
(5) cyclodehydration method by heating.
A compound (IVxe2x80x2-2) or (IVxe2x80x2-3) whose Z4 and Z5 are groups other than hydrogen atom may be obtained using a compound having a corresponding groups, respectively, as a raw material, or it may be derived from a compound whose Z4 and Z5 are both hydrogen atoms.
Usually, reactions of the above-mentioned compounds (Ixe2x80x2), (IIxe2x80x2), and (IIIxe2x80x2) and {(IVxe2x80x2-1), (IVxe2x80x2-2), or (IVxe2x80x2-3)} are performed at temperature of from 100 to 400xc2x0 C., and preferably from 200 to 350xc2x0 C.
A reaction time is usually adjusted by a melt viscosity of resulting polyimide esters, and is approximately several minutes to several tens of hours, and in order to restrain degradation of obtained polyimide esters, it is preferable in a range of several minutes to several hours.
Although catalysts are not necessarily required for the above-mentioned reaction, a suitable polymerization catalyst, such as sodium acetate, potassium acetate, pyridine, N-methyl imidazole, antimony trioxide, etc. may be added.
In an adding order of reaction raw materials, all of reaction raw materials may be mixed in a first stage, and, for example, a compound (Ixe2x80x2); and a mixture of a compound (IIxe2x80x2) and (IIIxe2x80x2), and ((IVxe2x80x2-1), (IVxe2x80x2-2), or (IVxe2x80x2-3)) may be reacted.
In addition, although the above-mentioned reaction is usually performed without using special solvents, if necessary; suitable solvent may be used.
As in the method described above, a polyimide ester of the present invention can be produced, and furthermore, after-treatments, such as well-known refining processing, can be performed for this polyimide ester to obtain a desired purity.
A polyimide ester of the present invention can be injection-molded at usual molding temperatures (no more than 400xc2x0 C.), and moreover, any molding methods used for general thermoplastic resins, such, as extrusion molding, compression molding, and spinning, can be applicable. Molded goods may be heat-treated at suitable temperature and in suitable period. Since a polyimide ester of the present invention has a small coefficient of linear expansion and small water absorbing property, and also has excellent heat resistance, it can be suitably used as a material of various fields, such as precision injection-molded products for electricity and electronic parts, filament, film, sheet, etc.